Rert-Butanol

Styrene is difficult to purify and keep pure. Usually contains added inhibitors (such as a trace of hydroquinone). Washed with aqueous NaOH to remove inhibitors (e.g. rert-butanol), then with water, dried for several hours with MgS04 and distd at 25° under reduced pressure in the presence of an inhibitor (such as 0.005% p-tert-butylcatechol). It can be stored at -78°. It can also be stored and kept anhydrous with Linde type 5A molecular sieves, CaH2, CaS04, BaO or sodium, being fractionally distd, and distd in a vacuum line just before use. Alternatively styrene (and its deuterated derivative) were passed through a neutral alumina column before use [Woon et al. J Am Chem Soc 108 7990 1986 Collman J Am Chem Soc 108 2588 1986]. 

Succinic acid [110-15-6] M 118.1, m 185-185.5 , pKf 4.21, pK 5.72. Washed with diethyl ether. Crystd from acetone, distd water, or rert-butanol. Dried under vacuum over P2O5 or cone H2SO4. Also... 

Surprisingly, the 2-tert-butyl group in 56 is also eliminated during this oxidation, with rert-butanol being a reaction product (76AP396). 

Poly(4-vinylpyridine) [25232-41-1] M (105.1) . Purified by repeated pptn from solns in EtOH and dioxane, and then EtOH and ethyl acetate. Finally, freeze-dried from rert-butanol. 

The potassium salts of 1,1-dinitroethane and 1,1-dinitropropane are also phenylated by diphenyliodonium tosylate (25) in rert-butanol under reflux (yields 67-68%). Poor yields were obtained when the reaction was performed in DMF (5%). 4... 

Ramirez and Marecek have investigated the solvolyses of 2,4-dinitrophenyl phosphate in aprotic and protic solvents and described reaction conditions that are consistent with the involvement of free metaphosphate anion 45, 46). In particular, the dianion of the reactive phosphate monoester is capable of transferring its phosphoryl group to /err-butanol whereas the monoanion of the same ester is essentially unreactive in the same reaction. Since rert-butanol is unreac-tive as a nucleophile for steric reasons, the phosphorylation of this alcohol is considered to be a diagnostic test for the involvement of the highly reactive metaphosphate anion. 

The laboratories of both Knowles and Cullis have described solvolysis conditions in which free metaphosphate anion can exist. Initially both laboratories investigated the possible stabilization of metaphosphate anion by acetonitrile, since this solvent was reported by Rebek et al. to allow a successful application of the three-phase text for free metaphosphate anion (44). The Harvard laboratory studied the reaction of phenyl (, 0, 0]phosphate with rert-butanol in acetonitrile (56), and the Leicester laboratory studied the reaction of [)8- 0, 0, 0]ADP with 2-0-benzyl-(5)-1,2-propanediol in acetonitrile (57). In both cases, complete racemization was observed, and this can be explained by the complexation of metaphosphate anion by the acetonitrile solvent. Thus, the success of the three-phase test of Rebek et al. for metaphosphate presumably can be attributed to diffusion of an acetonitrile-metaphosphate anion complex rather than free metaphosphate anion. 

Startg. steroidal l,4,7,9(ll)-tetraen-3-one allowed to react with HBr and acetic acid in rert-butanol equilenin. Y 95%. Also equilenin ethers in lower alcohols s. E. J. Bailey et al., Chem. Commun. 1967, 1253. 

D. rert.-Butanol-glacial acetic acid-water (60 6 34)... 

Preparative Method the title compound can be synthesized by reacting diethylmagnesium with rert-butanol in dry hexanes for 24 h. The solvent is then removed in vacuo to give a white powder. IR (KBr) cm 2972, 1473, 1385, 1361, 1205, 574, 499.2... 

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